The extremely high surface areas required for supercapacitors has limited the use of metal based electrodes, despite the other advantages such electrodes might have. Self-assembling surfactants and block co-polymers can be used as templates to produce nanostructured thin films that readily give 60-140 fold increases in surface area on both planar and three-dimensional substrates. However, even when relatively high surface area porous metal substrates such as nickel foam are used as a starting point, the resultant material still has surface area density well short of that available in other types of materials. Micro-emulsions offer a method of generating microstructure that bridges the gap between the 100 micron scale structures of foamed metals and the 10-50 nm scale structure of self-assembling block co-polymers. Electrodeposition of nickel and cobalt from micro-emulsions of Tween surfactants gives rise to structure on the 0.1-10 micron length scale. The scale of the microstructure is strongly influenced by the metal ion concentration and the potential at which the electrodeposition. The nature of the metal ion also strongly effects the ease with which the microstructure can be generated and the distribution of the microstructured film on foamed nickel electrodes. For microstructured nickel films ten fold surface area increases can be achieved. The microstructured films are expected to be compatible with a number of the nanostructuring methods to yield cumulative surface area increases of 1000-2000 fold.